U.S. patent application number 10/166128 was filed with the patent office on 2003-02-13 for composition in the form of a water-in-oil emulsion stabilized with a 2-acrylamido-2-methylpropanesulphonic acid (co) polymer containing hydrophobic grafts.
This patent application is currently assigned to L'OREAL. Invention is credited to Aubrun-Sonneville, Odile, L'alloret, Florence.
Application Number | 20030031643 10/166128 |
Document ID | / |
Family ID | 8864172 |
Filed Date | 2003-02-13 |
United States Patent
Application |
20030031643 |
Kind Code |
A1 |
L'alloret, Florence ; et
al. |
February 13, 2003 |
Composition in the form of a water-in-oil emulsion stabilized with
a 2-acrylamido-2-methylpropanesulphonic acid (CO) polymer
containing hydrophobic grafts
Abstract
A composition, in the form of a water-in-oil emulsion, is
characterized in that it contains at least one amphiphilic polymer
or copolymer of 2-acrylamido-2-methylpropanesulphonic acid bearing
hydrophobic grafts chosen from hydrocarbon-based radicals
containing from 6 to 30 carbon atoms, oxyalkylenated
hydrocarbon-based radicals comprising a hydrocarbon-based group
containing from 6 to 30 carbon atoms and at least one oxyalkylene
unit, and mixtures thereof.
Inventors: |
L'alloret, Florence; (Paris,
FR) ; Aubrun-Sonneville, Odile; (Antony, FR) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
8864172 |
Appl. No.: |
10/166128 |
Filed: |
June 11, 2002 |
Current U.S.
Class: |
424/70.16 ;
424/70.17 |
Current CPC
Class: |
A61K 8/064 20130101;
A61K 8/8158 20130101; A61Q 19/007 20130101; A61K 8/06 20130101 |
Class at
Publication: |
424/70.16 ;
424/70.17 |
International
Class: |
A61K 007/06; A61K
007/11 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 11, 2001 |
FR |
01 07609 |
Claims
1. A composition in the form of a water-in-oil emulsion comprising
an aqueous phase dispersed in an oily phase and an aqueous phase
stabilizing amount of at least one amphiphilic
2-acrylamido-2-methylpropanesulphonic acid polymer or copolymer
bearing hydrophobic grafts selected from hydrocarbon-based radicals
containing from 6 to 30 carbon atoms, oxyalkylenated
hydrocarbon-based radicals comprising a hydrocarbon-based group
containing from 6 to 30 carbon atoms and at least one oxyalkylene
unit, perfluoroalkyl radicals, silicon radicals, and mixtures
thereof, the molar degree of grafting with hydrophobic grafts of
the polymer or copolymer being at least equal to 50%.
2. The composition according to claim 1, wherein the molar degree
of grafting of the polymer or copolymer is greater than or equal to
60%.
3. The composition according to claim 1, wherein the
hydrocarbon-based radicals of the hydrophobic grafts contain from 6
to 22 carbon atoms.
4. The composition according to claim 1, wherein the
hydrocarbon-based radicals are selected from the group consisting
of linear or branched alkyl radicals, linear or branched alkenyl
radicals, alicyclic radicals, the cholesteryl radical and
cholesterol ester residues, and polycyclic aromatic radicals.
5. The composition according to claim 1, wherein the hydrophobic
grafts are oxyalkylenated hydrocarbon-based radicals comprising a
hydrocarbon-based group containing 6 to 22 carbon atoms and 1 to
100 oxyalkylene units.
6. The composition according to claim 5, wherein the oxyalkylenated
hydrocarbon-based radicals correspond to the formula: 7in which
R.sub.3 represents a C.sub.6-C.sub.30 hydrocarbon-based radical,
R.sub.4 represents hydrogen or a linear or branched C.sub.1-C.sub.6
alkyl group and n and p are, independently of each other, integers
from 0 to 100, with the proviso that the sum n+p, which is not
zero, is less than or equal to 100.
7. The composition according to claim 1, wherein the hydrophobic
grafts are covalently linked to the main chain of the polymer or of
the copolymer.
8. The composition of claim 7, wherein said hydrophobic grafts are
covalently linked via a functional bonding group chosen from ester,
amide, ether and urethane groups.
9. The composition according to claim 1, wherein the amphiphilic
copolymer containing hydrophobic grafts is a copolymer of
2-acrylamido-2-methylprop- anesulphonic acid and of at least one
ethylenically unsaturated monomer comprising a hydrophobic portion
chosen from hydrocarbon-based radicals containing from 6 to 30
carbon atoms, and oxyalkylenated hydrocarbon-based radicals
comprising a hydrocarbon-based radical as defined above,
perfluoroalkyl radicals and silicon radicals, and at least one
oxyalkylene unit.
10. The composition according to claim 9, characterized in that the
ethylenically unsaturated hydrophobic monomer corresponds to the
formula: 8in which R.sub.1 denotes a hydrogen atom, a linear or
branched C.sub.1-C.sub.6 alkyl radical; Y denotes O or NH or
NH--CO--O; R.sub.2 denotes a hydrophobic hydrocarbon-based radical
containing from 6 to 22 carbon atoms optionally further comprising
1 to 100 mol of oxyalkylenated units.
11. The composition according to claim 9, wherein the amphiphilic
copolymer is also a copolymer of at least one other ethylenically
unsaturated hydrophilic comonomer.
12. The composition according to claim 11, characterized in that
the hydrophilic comonomer is selected from the group consisting of
acrylic acid, methacrylic acid or alkyl derivatives thereof
substituted in the .beta. position or esters thereof obtained with
mono- or polyalkylene glycols, acrylamide, methacrylamide, itaconic
acid, styrene sulphonic acid, vinylsulphonic acid,
(meth)allylsulphonic acid, vinylphosphonic acid, N-vinylacetamide,
N-methyl N-vinylacetamide,.N-vinylformamide, N-methyl
N-vinylformamide, N-vinyllactames having an alkyle group having
from 4 to 9 carbon atoms, maleic anhydride, acrylonitrile, glycidyl
(meth)acrylate, vinyle chloride, vinylidene chloride,
methyldiallylammonium chloride, quaternized dimethylaminoethyl
methacrylate, (meth)acrylamidopropyl-trimethylammoniumchloride, and
methylvinylimidazolium chloride.
13. The composition according to claim 1, wherein the amphiphilic
copolymer containing hydrophobic grafts comprises: 0 to 45 mol % of
acrylamide units; 5 to 50 mol % of partially or totally neutralized
AMPS units; and 50 mol % or more of n(C.sub.6-C.sub.18)alkyl or
polyoxyethylenated alkyl units.
14. The composition according to claim 1, wherein the amphiphilic
copolymer containing hydrophobic grafts consists of: (a) from 5 to
50 mol % of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) units
of formula (2) below: 9in which X.sup.+ is a proton, an alkali
metal cation, an alkaline-earth metal cation, an ammonium ion or an
ammonium ion substituted with from 1 to 4 alkyl groups having from
1 to 15 carbon atoms; and (b) from 50 to 95 mol % of units of
formula (3) below: 10in which n and p, independently of each other,
denote a number of moles ranging from 0 to 100 with the proviso
that n+p is less than or equal to 100; R.sub.1 is a hydrogen atom
or a linear or branched C.sub.1-C.sub.6 alkyl radical and R.sub.3
denotes a linear or branched alkyl containing from 6 to 22 carbon
atoms.
15. The composition according to claim 1, wherein the amount of
polymer or copolymer represents 0.1% to 10% by weight relative to
the total weight of the composition.
16. The composition according to claim 1, characterized in that the
amphiphilic polymer or copolymer is in free or partially or totally
neutralized form.
17. The composition according to claim 1, wherein the amphiphilic
polymer or copolymer has a weight-average molecular weight of from
50 000 to 10 000 000 g/mole.
18. The composition according to claim 1, wherein the amphiphilic
polymer or copolymer is not crosslinked.
19. The composition according to claim 1, further comprising 1% by
weight or less of emulsifying surfactants relative to the total
weight of the composition.
20. The composition according to claim 1, comprising no emulsifying
surfactants.
21. The composition according to claim 1, wherein the oily phase
represents 2% to 60% by weight relative to the total weight of the
composition.
22. The composition according to claim 1, wherein the oily phase
comprises at least 5% by weight of hydrocarbon-based oils relative
to the total weight of the composition.
23. A method to treat, care for, make up, and/or cleanse facial
and/or body skin, mucous membranes, the scalp and/or keratin
fibers, comprising applying the composition of claim 1 to the skin,
mucous membranes, scalp and/or keratin fibers.
24. The method according to claim 23, wherein the composition
comprises no emulsifying agents.
25. The method according to claim 23, wherein the amount of polymer
or copolymer represents 0.1% to 10% by weight relative to the total
weight of the composition.
26. The method according to claim 23, wherein said composition
comprises 1% by weight or less of emulsifying surfactants relative
to the total weight of the composition.
27. The method according to claim 23, wherein said composition
comprises no emulsifying surfactants.
28. The method according to claim 23, wherein the oily phase
represents 2% to 60% by weight relative to the total weight of the
composition.
29. The method according to claim 23, wherein the oily phase
comprises at least 5% by weight of hydrocarbon-based oils relative
to the total weight of the composition.
30. The method of claim 23, wherein said composition is applied to
the keratin fibers.
31. The method of claim 23, wherein said composition is applied to
the skin.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to a composition,
preferably a cosmetic and/or dermatological composition in the form
of a water-in-oil emulsion, preferably free of emulsifying
surfactant or containing only a small amount of emulsifying
surfactant, comprising an aqueous phase stabilized in an oily phase
and a 2-acrylamido-2-methylprop- anesulphonic acid amphiphilic
polymer or copolymer preferably which is liposoluble or
lipo-dispersible or soluble or dispersible in a polar solvent.
Methods of preparing and using these compositions are also
disclosed and make up a part of the invention.
[0003] 2. Background of the Invention
[0004] Water-in-oil emulsions are dispersions of aqueous globules
in a continuous oily phase. These emulsions are generally
stabilized with amphiphilic molecules of low molar mass (<5000
g/mol) such as alkylglycerolated compounds, alkylpolyoxyethylenated
compounds or silicone compounds. These emulsions have the following
drawbacks:
[0005] the use of emulsifying surfactants that are relatively
aggressive with respect to the skin, and present at concentrations
of greater than 1% (by weight);
[0006] they are difficult to stabilize because the repulsive forces
between drops, of steric origin, are of low range. This is
reflected by a phenomenon of flocculation, which can give rise to
sedimentation and/or even coalescence;
[0007] silicone amphiphilic compounds are specific to oils of the
same nature, which limits the range of oils that may be used.
[0008] Silicone polymers for stabilizing water-in-oil emulsions
also exist; in this case, the oily phase must contain a predominant
amount of a silicone oil.
[0009] Patent application EP 1 069 142 A1 relates to water-soluble
polymers obtained by free-radical polymerization of at least one
macromonomer comprising a polyoxyalkylenated hydrophilic block and
a hydrophobic block that can contain from 1 to 30 carbon atoms with
at least one olefinically unsaturated comonomer comprising oxygen,
nitrogen, sulphur, phosphorus, chlorine and/or fluorine, in
particular acrylamidomethylpropanesulphonic acid. These polymers
may be used as thickeners, emulsifiers, dispersants, suspension
agents, stabilizers and/or consistency agents for an aqueous
preparation, especially in the cosmetic and/or pharmaceutical
fields.
OBJECT OF THE INVENTION
[0010] There is thus a need for a stable composition in the form of
a water-in-oil (W/O) emulsion, that can be used especially in
cosmetics and/or dermatology and that:
[0011] contains small amounts of emulsifying surfactant (that is to
say contains 1% or less by weight of emulsifying surfactant
relative to the total weight of the composition), preferably less
than 1% by weight, and better still contains none at all;
[0012] can contain hydrocarbon-based oils in large amounts (that is
to say 5% or more by weight relative to the total weight of the
composition); and
[0013] is stable with respect to flocculation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIGS. 1 and 2 show the water-in-oil emulsion obtained in
Example 1 at various magnifications.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The inventors has discovered, surprisingly, that polymers
and copolymers derived from 2-acrylamido-2-methylpropanesulphonic
acid (AMPS) and bearing hydrophobic grafts chosen from
C.sub.6-C.sub.30 hydrocarbon-based radicals, the C.sub.6-C.sub.30
hydrocarbon-based radicals comprising at least one oxyalkylene
unit, prefluoroalkyl radicals, silicon radicals, and mixtures
thereof, make it possible to obtain water-in-oil emulsions that do
not flocculate and that can contain large amounts of
hydrocarbon-based oils. The molar degree of grafting with
hydrophobic graft of the polymers is greater than or equal to 50%
(50% or more), preferably greater than or equal to 60% (60% or
more) and better still 65% (65% or more).
[0016] Thus, one subject of the invention is a composition,
preferably a cosmetic and/or dermatological composition, in the
form of a water-in-oil emulsion comprising an aqueous phase
dispersed in an oily phase and an amount, to stabilize the aqueous
phase, of at least one amphiphilic
2-acrylamido-2-methylpropanesulphonic acid polymer or copolymer
bearing hydrophobic grafts chosen from hydrocarbon-based radicals
containing from 6 to 30 carbon atoms, oxyalkylenated
hydrocarbon-based radicals comprising a hydrocarbon-based group
containing from 6 to 30 carbon atoms and at least one oxyalkylene
unit, perfluoroalkyl radicals, silicon radicals and mixtures
thereof, the molar degree of grafting with hydrophoblic graft of
the polymer or copolymer being at least equal to 50%.
[0017] A subject of the invention is also the use, in a composition
such as a cosmetic and/or dermatological composition, in the form
of a water-in-oil emulsion comprising an aqueous phase dispersed in
an oily phase, as an agent for stabilizing the aqueous phase, of a
stabilizing amount of at least one amphiphilic
2-acrylamido-2-methylpropanesulphonic acid polymer or copolymer
bearing hydrophobic grafts chosen from hydrocarbon-based radicals
containing from 6 to 30 carbon atoms, oxyalkylenated
hydrocarbon-based radicals comprising a C.sub.6-C.sub.30
hydrocarbon-based group and at least one oxyalkylene unit
perfluoroalkyl radicals, silicon radicals, and mixtures thereof,
the molar degree of grafting with hydrophobic graft of the polymer
or copolymer being at least equal to 50%.
[0018] The polymers and copolymers of the invention are liposoluble
or lipo-dispersible derivatives of
2-acrylamido-2-methylpropanesulphonic acid (AMPS), bearing alkyl
and/or alkylpolyoxyalkylenated grafts and/or perfluoroalkyl radical
and/or silicon radical. The molar degree of grafting of these
grafts is greater than or equal to 50%, preferably greater than or
equal to 60% and better still greater than or equal to 65%, such as
for example 70%, 75%, 80%, 85%, 90%, 95%, etc.
[0019] The expression "soluble or dispersible in a polar solvent
polymers and copolymers" means polymers and copolymers which, when
introduced into a polar solvent, at a concentration equal to 1% by
weight, with stirring at 50.degree. C. for 48 hours, give a
macroscopically homogeneous solution and preferably whose light
transmittance may be, at a wavelength equal to 500 nm through a
sample 1 cm thick, is at least 50% and preferably at least 60%.
[0020] The expression "polar solvent" means a solvent having a
dielectric constant measured at 25.degree. C., less than 50. This
solvent may be especially chosen from lower alcohols having from 1
to 6 carbon atoms, such as ethanol (dielectric constant: 24.6);
ketones such as acetone (dielectric constant: 20.7); polyols such
as propylene glycol (dielectric constant: 30.2); ethers such as
diethylether (dielectric constant: 4.3), and their mixtures.
[0021] The polymers and copolymers in accordance with the invention
are amphiphilic 2-acrylamido-2-methylpropanesulphonic acid (AMPS)
polymers and copolymers.
[0022] The expression "amphiphilic polymer and copolymer" means any
polymer or copolymer comprising both a hydrophilic portion and a
hydrophobic portion.
[0023] The hydrophobic portion present in the polymers and
copolymers of the invention corresponds to the lateral fatty chains
or hydrophobic grafts.
[0024] The hydrophobic grafts are covalently linked to the main
backbone of the polymer or copolymer, preferably via a functional
bonding group, for example an ester, amide, ether or urethane
group.
[0025] The hydrophobic grafts are chosen from C.sub.6-C.sub.30,
preferably C.sub.6-C.sub.22 and better still C.sub.12-C.sub.18
hydrocarbon-based radicals, the hydrocarbon-based radicals defined
above and also comprising at least one oxyalkylene unit, generally
1 to 30 oxyalkylene units, preferably 1 to 25 oxyalkylene units and
better still from 3 to 20 oxyalkylene units, in particular
oxyethylene or oxypropylene units, perfluoroalkyl radicals, silicon
radicals, and mixtures of these units.
[0026] Included among the hydrocarbon-based radicals that are
suitable for the hydrophobic grafts according to the invention
are:
[0027] linear or branched alkyl radicals, for example n-hexyl,
n-octyl, n-decyl, n-hexadecyl, n-dodecyl and isostearyl;
[0028] linear or branched alkenyl radicals, for example oleyl;
[0029] alicyclic radicals, for example cyclododecane and
adamantane;
[0030] the cholesteryl radical and cholesterol ester residues, for
example the cholesteryl oxyhexanoate group;
[0031] polycyclic aromatic radicals, for example naphthyl and
pyrenyl radicals.
[0032] As perfluoroalkyl radicals, included in particular are
C.sub.6-C.sub.18 radicals, for example the radical of formula:
1
[0033] The silicon radicals include polydimethylsiloxanes (PDMS)
having a molecular weight lower than 20,000 g/mole.
[0034] The hydrophobic grafts that are preferred are linear or
branched, such as the n-dodecyl and n-hexadecyl radicals and
isostearyl radicals, or alkenyl radicals such as oleyl.
[0035] Among the hydrocarbon-based radicals comprising 1 to 100
oxyalkylene units, mention may be made of the radicals of formula:
2
[0036] in which R.sub.3 represents a C.sub.6-C.sub.30
hydrocarbon-based radical as defined above, R.sub.4 represents
hydrogen or a linear or branched C.sub.1-C.sub.6 alkyl group
(preferably methyl) and n and p are, independently of each other,
integers from 0 to 100, preferably 1 to 30 and better still from 3
to 20, with the proviso that the sum n+p, which is not zero, is
less than or equal to 100, preferably less than 30 and better still
less than 20.
[0037] The polymers and copolymers in accordance with the invention
are preferably partially or totally neutralized with a mineral base
(for example sodium hydroxide, potassium hydroxide or aqueous
ammonia or ammonium substituted with from 1 to 4 alkyl groups
having from 1 to 15 carbon atoms) or an organic base such as
monoethanolamine, diethanolamine, triethanolamine, an
aminomethylpropanediol, N-methylglucamine, basic amino acids, for
instance arginine and lysine, and mixtures thereof.
[0038] The polymers and copolymers in accordance with the invention
generally have a weight-average molecular weight ranging from
50,000 to 10,000,000 g/mole, more preferably from 100,000 to
8,000,000 g/mole and even more preferably from 100,000 to 7,000,000
g/mole.
[0039] The amphiphilic AMPS polymers and copolymers according to
the invention may be crosslinked or non-crosslinked. They are
preferably non-crosslinked.
[0040] The crosslinking agents include compounds containing
olefinic polyunsaturation commonly used for crosslinking polymers
obtained by free-radical polymerization. Examples that may be
mentioned include divinylbenzene, diallyl ether, dipropylene glycol
diallyl ether, polyglycol diallyl ethers, triethylene glycol
divinyl ether, hydroquinone diallyl ether, tetraallyl-oxyethanoyl
or other polyfunctional allyl or vinyl alcohol ethers,
tetraethylene glycol diacrylate, triallylamine, trimethylolpropane
diallyl ether, tetraallyloxyethane, methylenebisacrylamide, allylic
ethers of alcohols of the sugar series, allyl methacrylate,
trimethylolpropane triacrylate (TMPTA), or mixtures thereof.
[0041] Methylenebisacrylamide, allyl methacrylate or
trimethylolpropane triacrylate (TMPTA) will be used more
particularly. The degree of crosslinking can preferably range from
0.01 mol % to 10 mol % and more particularly from 0.2 mol % to 2
mol % relative to the polymer or copolymer.
[0042] The polymers in accordance with the invention may be chosen
especially from random amphiphilic AMPS polymers modified by
reaction with a C.sub.6-C.sub.22 n-monoalkylamine or
di-n-alkylamine, such as those described in patent application
WO-A-00/3 1154 (forming an integral part of the content of this
description and being incorporated herein by reference). These
polymers may also contain other ethylenically unsaturated
hydrophilic monomers chosen, for example, from acrylic acid,
methacrylic acid or alkyl derivatives thereof substituted in the
.beta. position or esters thereof obtained with mono- or
polyalkylene glycols, acrylamide, methacrylamide, itaconic acid,
styrene sulphonic acid, vinylsulphonic acid, (meth)allylsulphonic
acid, vinylphosphonic acid, N-vinylacetamide, N-methyl
N-vinylacetamide, N-vinylformamide, N-methyl N-vinylformamide,
N-vinyllactames having an alkyle group having from 4 to 9 carbon
atoms, such as N-vinylpyrrolidone, N-butyrolactame and
N-vinylcaprolactame, maleic anhydride, acrylonitrile, glycidyl
(meth)acrylate, vinyle chloride, vinylidene chloride,
methyldiallylammonium chloride, quaternized dimethylaminoethyl
methacrylate (MADAME), (meth)acrylamidopropyl-trimethylammonium
chloride (APTAC and MAPTAC), methylvinylimidazolium chloride, or
mixtures thereof.
[0043] The preferred copolymers of the invention are chosen from
amphiphilic copolymers of AMPS and of at least one ethylenically
unsaturated monomer comprising at least one hydrophobic portion
containing from 6 to 30 carbon atoms, preferably from 6 to 22
carbon atoms, more preferably from 6 to 18 carbon atoms and more
particularly from 12 to 18 carbon atoms.
[0044] These same copolymers can also contain one or more
ethylenically unsaturated hydrophilic comonomers, for instance
acrylic acid, methacrylic acid or alkyl derivatives thereof
substituted in the P position or esters thereof obtained with mono-
or polyalkylene glycols, acrylamide, methacrylamide, itaconic acid,
styrene sulphonic acid, vinylsulphonic acid, (meth)allylsulphonic
acid, vinylphosphonic acid, N-vinylacetamide, N-methyl
N-vinylacetamide, N-vinylformamide, N-methyl N-vinylformamide,
N-vinyllactames having an alkyle group having from 4 to 9 carbon
atoms, such as N-vinylpyrrolidone, N-butyrolactame and
N-vinylcaprolactame, maleic anhydride, acrylonitrile, glycidyle
(meth)acrylate, vinyle chloride, vinylidene chloride,
methyldiallylammonium chloride, quaternized dimethylaminoethyl
methacrylate (MADAME), (meth)acrylamidopropyl-trimethylammonium
chloride (APTAC et MAPTAC), methylvinylimidazolium chloride.
[0045] The ethylenically unsaturated hydrophobic monomers of these
specific copolymers are preferably chosen from the acrylates and
acrylamides of formula (1) below: 3
[0046] in which R.sub.1 denotes a hydrogen atom, a linear or
branched C.sub.1-C.sub.6 alkyl radical (preferably methyl); Y
denotes O or NH or NH--CO--O; R.sub.2 denotes a hydrophobic
hydrocarbon-based radical containing from 6 to 22 carbon atoms,
preferably from 6 to 18 and more particularly from 12 to 18 carbon
atoms.
[0047] The hydrophobic radical R.sub.2 is preferably chosen from
C.sub.6-C.sub.18 alkyl and alkenyl radicals, that are linear (for
example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl or
oleyl), branched (for example isostearyl) or alicyclic (for example
cyclododecane or adamantane), C.sub.6-C.sub.18 perfluoroalkyl
radicals, for example the group of formula 4
[0048] the cholesteryl radical or a cholesterol ester, for instance
cholesteryl hexanoate; aromatic polycyclic groups, for instance
naphthalene or pyrene. Among these radicals, the ones that are more
particularly preferred are the linear and branched alkyl
radicals.
[0049] According to one particularly preferred form of the
invention, the hydrophobic radical R.sub.2 also comprises at least
one alkyleneoxide unit and preferably a polyoxyalkylenated chain.
The polyoxyalkylenated chain preferably consists of ethyleneoxide
units and/or of propyleneoxide units and even more particularly
consists solely of ethyleneoxide units. The number of moles of
oxyalkylenated units generally ranges from 1 to 100 mol and
preferably from 1 to 30 mol and more preferably from 3 to 20
mol.
[0050] Among these copolymers that may be mentioned are copolymers
comprising from 0 to 45 mol % of acrylamide units, from 5 to 50 mol
% of partially or totally neutralized AMPS units and comprising at
least 50 mol % of units having a (C.sub.6-C.sub.18)alkyl or
polyoxyethylenated alkyl chain, preferably at least 60% and better
still at least 65%.
[0051] Included are polymers comprising:
[0052] (a) from 5 to 50 mol % of
2-acrylamido-2-methylpropanesulphonic acid (AMPS) units of formula
(2) below: 5
[0053] in which X.sup.+ is a proton, an alkali metal cation, an
alkaline-earth metal cation, an ammonium ion or an ammonium ion
substituted with from 1 to 4 alkyl groups having from 1 to 15
carbon atoms; and
[0054] (b) from 50 to 95 mol % of units of formula (3) below: 6
[0055] in which n and p, independently of each other, denote a
number of moles ranging from 0 to 100, preferably from 1 to 30 and
more preferably from 3 to 20, with the proviso that n+p is less
than or equal to 100, preferably less than 30 and better still less
than 20; R.sub.1 has the same meaning indicated above for formula
(1) and R.sub.3 denotes a linear or branched alkyl containing from
6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms and
better still from 12 to 18 carbon atoms.
[0056] The stabilizing amount of polymer or copolymer is any amount
that is sufficient to give the W/O emulsion the required stability,
in particular that is sufficient to avoid the phenomenon of
flocculation of the emulsion (destabilization).
[0057] The amount of the polymers and copolymers used in accordance
with the invention is not limited. These polymers and copolymers
are generally present in the invention compositions in
concentrations by weight ranging from 0.1% to 10%, preferably from
0.5 to 8% and better still from 1% to 5% relative to the total
weight of the composition.
[0058] The non-flocculated nature of the emulsions may be
demonstrated by optical microscopy, after dilution, if necessary,
when the emulsions are concentrated. A non-flocculated emulsion
consists of drops that are independent of each other; a flocculated
emulsion comprises aggregates of drops, which is not observed in
the compositions of the invention.
[0059] The fatty phase or oily phase usually contains at least one
oil. As oils that may be used in the composition of the invention,
mention may be made, for example, of: hydrocarbon-based oils of
animal origin, such as perhydrosqualene;
[0060] hydrocarbon-based oils of plant origin, such as liquid
triglycerides of fatty acids containing from 4 to 22 carbon atoms,
for instance heptanoic or octanoic acid triglyceride or
alternatively, for example, sunflower oil, corn oil, soybean oil,
marrow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil,
macadamia oil, arara oil, sunflower oil, castor oil, avocado oil,
caprylic/capric acid triglycerides for instance those sold by the
company Stearineries Dubois or those sold under the names Miglyol
810, 812 and 818 by the company Dynamit Nobel, jojoba oil or karite
butter oil;
[0061] synthetic esters and synthetic ethers, especially of fatty
acids, for instance oils of formulae R'COOR" and R'OR" in which R'
represents a fatty acid residue containing from 8 to 29 carbon
atoms and R" represents a branched or unbranched hydrocarbon-based
chain containing from 3 to 30 carbon atoms, such as, for example,
purcellin oil, isononyl isononanoate, isopropyl myristate,
2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl
erucate or isostearyl isostearate; hydroxylated esters such as
isostearyl lactate, octyl hydroxystearate, octyldodecyl
hydroxystearate, diisostearyl malate, triisocetyl citrate and fatty
alcohol heptanoates, octanoates and decanoates; polyol esters, for
instance propylene glycol dioctanoate, neopentyl glycol
diheptanoate and diethylene glycol diisononanoate; and
pentaerythritol esters, for instance pentaerythrityl
tetraisostearate;
[0062] linear or branched hydrocarbons of mineral or synthetic
origin, such as volatile or non-volatile liquid paraffins, and
derivatives thereof, petroleum jelly, polydecenes, and hydrogenated
polyisobutene such as Parleame oil;
[0063] fatty alcohols containing from 8 to 26 carbon atoms, for
instance cetyl alcohol, stearyl alcohol and a mixture thereof
(cetylstearyl alcohol), octyldodecanol, 2-butyloctanol,
2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl
alcohol;
[0064] alkoylated and especially ethoxylated fatty alcohols or
fatty acids, such as oleth-12 and PEG-20 stearate;
[0065] partially hydrocarbon-based and/or silicone-based fluoro
oils, for instance those described in document JP-A-2 295 912.
Examples of fluoro oils which may also be mentioned include
perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane,
sold under the names "Flutec PC1.RTM." and "Flutec PC3.RTM." by the
company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane;
perfluoroalkanes such as dodecafluoropentane and
tetradecafluorohexane, sold under the names "PF 5050.RTM." and "PF
5060.RTM." by the company 3M, or alternatively bromoperfluorooctyl
sold under the name "Foralkyl.RTM." by the company Atochem;
nonafluoromethoxybutane sold under the name "MSX 4518.RTM." by the
company 3M and nonafluoroethoxyisobutane; perfluoromorpholine
derivatives, such as the 4-trifluoromethylperfluoromorpholine sold
under the name "PF 5052.RTM." by the company 3M;
[0066] silicone oils, for instance volatile or non-volatile
polymethylsiloxanes (PDMSs) containing a linear or cyclic silicone
chain, that are liquid or pasty at room temperature, especially
cyclopolydimethylsiloxanes (cyclomethicones) such as
cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy
or phenyl groups, that are pendent or at the end of a silicone
chain, these groups containing from 2 to 24 carbon atoms;
phenylsilicones, for instance phenyltrimethicones,
phenyldimethicones, phenyltrimethylsiloxy-diphenylsiloxanes,
diphenyldimethicones, diphenylmethyldiphenyltrisiloxanes,
2-phenylethyltrimethylsiloxysilicates and mixtures thereof.
[0067] In the list of oils mentioned above, the expression
"hydrocarbon-based oil" means any oil mainly comprising carbon and
hydrogen atoms, and optionally ester, ether, fluoro, carboxylic
acid and/or alcohol groups.
[0068] Other fatty substances that may be present in the oily phase
include, for example, fatty acids containing from 8 to 30 carbon
atoms, for instance stearic acid, lauric acid, palmitic acid and
oleic acid; waxes, for instance lanolin, beeswax, carnauba wax or
candelilla wax, paraffin wax, lignite wax or microcrystalline
waxes, ceresin or ozokerite, synthetic waxes such as polyethylene
waxes, Fischer-Tropsch waxes; gums such as silicone gums
(dimethiconol); silicone resins such as
trifluoromethyl-C.sub.1-4-alkyldimethicone and
trifluoropropyldimethicone- ; and silicone elastomers, for instance
the products sold under the names "KSG" by the company Shin-Etsu,
under the names "Trefil", "BY29" or "EPSX" by the company Dow
Corning or under the names "Gransil" by the company Grant
Industries and other known and yet to be discovered gelifying
agents of an oily phase.
[0069] These fatty substances may be chosen in a varied manner by a
person skilled in the art so as to prepare a composition having the
desired properties, for example in terms of consistency or
texture.
[0070] The amount of oily phase in the emulsion of the invention is
not limited and can range, for example, from 2% to 5%, preferably
from 5% to 50% and better still from 10% to 40% by weight relative
to the total weight of the composition.
[0071] In a known manner, the composition of the invention can also
contain adjuvants that are new or common in cosmetics and/or
dermatology, other than those mentioned above, such as solvents,
active agents, preserving agents, antioxidants, complexing agents,
fragrances, organic or mineral UV filters (screening agents),
salts, fillers, bactericides, odour absorbers, dyestuffs and lipid
vesicles. The amounts of these various adjuvants may be those
conventionally used in the field under consideration, and, for
example, from 0.01% to 20% relative to the total weight of the
composition. Depending on their nature, these adjuvants may be
introduced into the fatty phase, into the aqueous phase and/or into
the lipid vesicles. Needless to say, a person skilled in the art
will take care to select the optional additional additives and/or
the amount thereof such that the advantageous properties of the
composition according to the invention are not, or are not
substantially, adversely affected by the envisaged addition.
[0072] Active agents that may be used in the composition of the
invention include, for example, moisturizers and, for example,
protein hydrolysates and polyols such as glycerol, glycols, for
instance polyethylene glycols, and sugar derivatives; natural
extracts; procyannidol oligomers; vitamins, for instance vitamin A
(retinol), vitamin C (ascorbic acid), vitamin E (tocopherol),
vitamin B5 (panthenol) and vitamin B3 (niacinamide); urea;
caffeine; depigmenting agents such as cogic acid and caffeic acid;
salicylic acid; .alpha.-hydroxy acids such as lactic acid and
glycolic acid; retinoids such as carotenoids; hydrocortisone;
melatonin; extracts of algae, of fungi, of plants, of yeasts or of
bacteria; hydrolysed, partially hydrolysed or unhydrolysed
proteins, and enzymes; DHEA and derivatives and metabolites
thereof; antibacterial active agents for treating greasy skin, for
instance 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or tricolosan)
and 3,4,4'-trichlorocarbanilide (or triclocarban); matt-effect
agents, for instance fibres; sunscreens, and mixtures thereof.
[0073] As organic UV sunscreens, included are, for example:
[0074] Butylmethoxydibenzoylmethane sold especially by HOFFMANN LA
ROCHE under the name PARSOL 1789,
[0075] octocrylene sold especially by BASF under the name UVINUL
N539,
[0076] octylsalicylate sold especially by Haarman-Reimer under the
name Neo Heliopan OS,
[0077] octylmethoxycinnamate sold especially by Hoffmann Laroche
under the name PARSOL MCX,
[0078] phenylbenzimidazole sulphonic acid sold especially by Merck
under the name Eusolex 232,
[0079] oxybenzones such as benzophenones-3, -4 ou -5,
[0080] benzotriazoles silicones and in particular drometrizole
trisiloxane, and those described in the document
FR-A-2,642,968,
[0081] terephtalylidene di-camphor sulphonic, in particular Mexoryl
SX sold by Chimex,
[0082] and the insoluble organic sunscreens such as triazine
derivatives, and, in particular 2,4-bis
([4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl)-6-(4-
-methoxy-phenyl)-1,3,5-triazine sold by CIBA GEIGY under the name
TINOSORB S, and 2,2'-methylenebis-[6-(2H benzotriazol-2-yl)
4-(1,1,3,3-tetramethylbutyl)-phenol] sold by CIBA GEIGY under the
name TINOSORB M.
[0083] As physic UV sunscreens, mention may be made, for example,
of titan or zinc oxides, as microparticules or nanoparticules
(nanopigments) which are eventually coated.
[0084] The active agent(s) may be present, for example, in a
concentration ranging from 0.01% to 20%, preferably from 0.1% to
10% and better still from 0.5% to 5% relative to the total weight
of the composition.
[0085] Useful fillers which may be used in the composition of the
invention include for example, besides pigments, silica powder;
talc; polyamide particles and especially those sold under the name
Orgasol by the company Atochem; polyethylene powders; microspheres
based on acrylic copolymers, such as those based on ethylene glycol
dimethacrylate/lauryl methacrylate copolymer sold by the company
Dow Corning under the name Polytrap; expanded powders such as
hollow microspheres and especially the microspheres sold under the
name Expancel by the company Kemanord Plast or under the name
Micropearl F 80 ED by the company Matsumoto; powders of natural
organic materials such as crosslinked or noncrosslinked corn
starch, wheat starch or rice starch, such as the powders of starch
crosslinked with octenyl succinate anhydride, sold under the name
Dry-Flo by the company National Starch; silicone resin microbeads
such as those sold under the name Tospearl by the company Toshiba
Silicone; latex; and mixtures thereof. These fillers may be present
in amounts ranging from 0.01% to 20% by weight and preferably from
0.1% to 10% by weight and better 0.5 A 5% by weight relative to the
total weight of the composition.
[0086] The composition of the invention may eventually contain also
surfactants, for example cleansing surfactants (which are foaming
surfactants and not emulsifying surfactants) and especially non
ionic surfactants such as ethoxylated or glycerolated fatty
alcohols or acids; anionic surfactants such as alkyl ether
sulphonates or alkyl ether sulphates, or phosphate esters or
ethers; cationic surfactants such as salts of cationic fatty acid
such as Esterquats; amphoteric and zwitterionic surfactants such as
betaines; and mixtures thereof.
[0087] Furthermore, the composition of the invention may contain in
the aqueous phase, one or several hydrophilic polymers chosen for
example from carboxyvinylic polymers such as carbopols (carbomers);
polymers of 2-acrylamido-2-methylpropane sulphonic acid which are
soluble or dispersible in aqueous phase such as the polymer
marketed under the name <<Hostacerin AMPS>> (INCI name:
ammonium polyacryldimethyl-tauramide), by Clariant; synthetic
neutral polymers such as polyvinylpyrrolidone (PVP), polyvinyl
acetate (PVA); polysaccharides such as guar or xanthane gums and
cellulosic derivatives; hydrosoluble ou hydrodispersible silicone
derivatives such as acrylic silicones and cationic silicones; and
mixtures thereof. The polymer or the polymers may be present in a
concentration from 0.01 to 20%, preferably from 0.05 to 10% and
better from 0.1 to 5% of the total weight of the composition.
[0088] The compositions according to the invention are preferably
in the form of water-in-oil emulsions of liquid to semi-liquid
consistency, such as milks, more or less unctuous creams,
cream-gels or pastes. They may optionally be packaged as aerosols
and may be in the form of a mousse or a spray.
[0089] Advantageously, according to one particular embodiment of
the invention, the emulsions prepared with the polymers and/or
copolymers according to the invention may comprise only 1% by
weight or less, or may even be free of, emulsifying surfactants,
while at the same time being stable on storage.
[0090] The composition according to the invention may be used in
many cosmetic or dermatological applications, and in particular it
may be used to treat, care for and/or makeup and/or cleanse facial
and/or body skin, mucous membranes (lips), the scalp and/or keratin
fibres (hair or eyelashes), for example to give the face a light
and radiant complexion, a healthy look, a smooth and younger
appearance, to treat skin wrinkles and fine lines, to depigment the
skin and especially to remove age marks, to eliminate comedones, to
treat damaged hair, tonify it and restore its vitality, and to
strengthen keratin fibres.
[0091] Thus, the compositions of the invention may be used as care
and/or hygiene products, such as protective, treatment or care
creams for the face, for the hands or for the body, protective or
care body milks, lotions, gels or mousses to care for the skin and
mucous membranes or to cleanse (including makeup removal) or scrub
the skin. They may also constitute make-up products for keratin
fibres, for the skin, for the lips and/or for the nails. They may
especially constitute a foundation, a face powder, an eyeshadow, a
lipstick, a mascara or an eyeliner.
[0092] The compositions of the invention may also be used as
antisun products for protecting the skin against UV rays.
[0093] The compositions according to the invention may be used as
rinse-out or leave-in hair products, especially for washing, caring
for, conditioning or maintaining the hairstyle or for shaping
keratin fibres such as the hair. They may also consist of solid
preparations constituting soaps or cleansing bars.
[0094] The compositions of the invention may also be used as
buccodental care products, such as toothpastes.
[0095] They may also be styling products such as hairsetting
lotions, blow-drying lotions and fixing or styling compositions.
The lotions may be packaged in various forms, especially in
vaporizers, pump-dispenser bottles or in aerosol containers so as
to be able to apply the composition in vaporized form or in the
form of a mousse. Such packaging forms are indicated, for example,
when it is desired to obtain a spray or a mousse for fixing or
treating the hair.
[0096] Thus, a subject of the present invention is also the
cosmetic use of the composition according to the invention to
treat, care for, make up and/or cleanse facial and/or body skin,
mucous membranes (lips), the scalp and/or keratin fibres.
[0097] Another subject of the invention is a cosmetic process for
treating human keratin materials such as the skin, including the
scalp, the hair, the eyelashes, the eyebrows, the nails or mucous
membranes, especially the lips, characterized in that a cosmetic
composition as defined above is applied to the keratin materials,
according to the usual technique for using this composition. For
example, application of creams, gels, sera, lotions or milks to the
skin, the scalp and/or mucous membranes. The type of treatment
depends on the active agent(s) present in the composition.
[0098] A subject of the invention is also a use of the above
composition to prepare a salve or an ointment for treating the
human face and/or body, including the hands, especially to treat
acne.
[0099] Finally, a method of preparing the invention compositions is
also a subject of the invention, and comprises mixing together the
invention (co)polymer(s) and the emulsion components in any order
of addition or contact.
[0100] The examples that follow illustrate the present invention
but do not limit it. In the examples, except where otherwise
indicated, all the percentages and parts are expressed on a weight
basis.
EXAMPLE 1
Care Cream
[0101] In this example, an AMPS copolymer comprising (C.sub.12-14)
alkyl grafts containing 3 oxyethylenated units (molar degree of
grafting=69%) is used, a 1% solution of which in a mixture of
tocopheryl acetate (13.3% by weight) and 60/40 C.sub.8-10
caprylic/capric triglycerides (86.7%) has a light transmittance, at
a wavelength of 500 nm, equal to 68%. This transmittance
measurement is carried out using a Cary 300 spectrophotometer
(Varian), using cuvettes 1 cm thick.
1 % Oily phase AMPS copolymer comprising C.sub.12-14 grafts, 3
oxyethylenated units 2.5 (molar degree of grafting = 69%)
Tocopheryl acetate 3 60/40 C.sub.8-10 caprylic/capric triglycerides
19.5 Aqueous phase Glycerol 3 Magnesium sulphate 2.25 Preserving
agent 0.07 Demineralized water 69.68
[0102] Preparation Method
[0103] The AMPS amphiphilic copolymer is dissolved for 48 hours
with stirring in the oily phase at 50.degree. C.; the solution
obtained is macroscopically homogeneous. The emulsion is prepared
by slowly introducing the aqueous phase into the oily phase with
stirring using a Moritz homogenizer at a stirring speed of 1500
rpm.
[0104] The size of the drops in the emulsion obtained is between
100 nm and 2 microns. The viscosity at a shear rate of 200 s.sup.-1
is equal to 1.4 Pa.s (measured using a Haake RS 150 rheometer
equipped with a 6 cm/2.degree. cone/plate geometry at about
25.degree. C.).
[0105] FIGS. 1 and 2 are photographs of the water-in-oil emulsion
obtained, taken using an optical microscope in interference
contrast mode, at magnifications of .times.400 (FIG. 1) and
.times.1 000 (FIG. 2).
[0106] As shown in FIGS. 1 and 2, the emulsion is not flocculated,
and has a beautiful texture of cream type, that is relatively
non-greasy and pleasant to apply.
EXAMPLE 2
Milk for Dry Skin
[0107] In this example, an AMPS copolymer comprising C.sub.12-14
grafts and 3 oxyethylenated units (molar degree of grafting=69%) is
used, a 1% solution of which in a mixture of tocopheryl acetate
(13.3% by weight) and 60/40 C.sub.8-10 caprylic/capric
triglycerides (86.7%) has a light transmittance, at a wavelength of
500 nm, equal to 68%. This transmittance measurement is carried out
using a Cary 30 spectrophotomer (Varian), using cuvettes 1 cm
thick.
2 % Oily phase AMPS copolymer comprising C.sub.12-14 grafts, 3
oxyethylenated units 2.5 (molar degree of grafting = 69%)
Tocopheryl acetate 3 60/40 C.sub.8-10 caprylic/capric triglycerides
25.5 Oily gelling agent 4 Aqueous phase Glycerol 3 Magnesium
sulphate 1.95 Preserving agent 0.06 Demineralized water 59.99
[0108] Preparation Method
[0109] The AMPS amphiphilic copolymer is dissolved for 48 hours
with stirring in the oily phase at 50.degree. C.; the solution
obtained is macroscopically homogeneous. The emulsion is prepared
by slowly introducing the aqueous phase into the oily phase with
stirring using a Moritz homogenizer at a stirring speed of 1500
rpm.
[0110] The size of the drops is about 1 micron. The viscosity at a
shear rate of 200 s.sup.-1 is equal to 0.6 Pa.s (measured using a
Haake RS 150 rheometer equipped with a 6 cm/2.degree. cone/plate
geometry at about 25.degree. C.).
[0111] The emulsion is not flocculated and has a beautiful fluid
texture suitable for a body milk, of dry-skin type.
COMPARATIVE EXAMPLE
[0112] In this counter-example, an AMPS copolymer comprising
isostearic grafts and 20 oxyethylenated units (molar degree of
grafting=40.8%) is used, a 1% solution of which in a mixture of
tocopheryl acetate (13.3% by weight) and 60/40 C.sub.8-10
caprylic/capric triglycerides (86.7%) has a light transmittance, at
a wavelength of 500 nm, equal to 2%. This transmittance measurement
is carried out using a Cary 300 spectrophotomer (Varian), using
cuvettes 1 cm thick.
3 % Oily phase AMPS copolymer comprising isostearic grafts and 2.5
20 oxyethylenated units (molar degree of grafting = 40.8%)
Tocopheryl acetate 3 60/40 C.sub.8-10 caprylic/capric triglycerides
24.5 Oily gelling agent 4 Aqueous phase Glycerol 3 Preserving agent
0.07 Demineralized water 66.93
[0113] Preparation Method
[0114] The AMPS amphiphilic copolymer is introduced for 48 hours
with stirring into the oily phase at 50.degree. C.; the solution
obtained contains undissolved polymer aggregates, that can be seen
visually. After 24 hours at rest, this solution contains sedimented
polymer aggregates. The emulsion is prepared by slowly introducing
the aqueous phase into the oily phase with stirring using a Moritz
homogenizer at a stirring speed of 1500 rpm.
[0115] The emulsion obtained is of oil-in-water type, rather than
water-in-oil type as in the examples according to the
invention.
[0116] French Patent Application 0107609 filed Jun. 11, 2001 is
incorporated herein by reference, as are all documents, texts,
standards, references, patents and applications referred to
above.
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